JPH0624768A - Natural marble-like crystallized glass article and its production - Google Patents

Abstract

PURPOSE:To obtain the title glass article of high flexural strength, thin thickness and light weight by acuumulating small lumps of glass depositing beta-wallastonite or diopside on a glass plate and heat-treating them to fuse melt the lumps onto the plate integrally. CONSTITUTION:A glass formulation of 45 to 70wt.% of SiO2; 1 to 13wt.% of Al2O3; 6 to 25wt.% of Cab; 0.1 to 20wt.% of Na2O+K2O+Li2O; 0 to 20wt.% of BaO; 0 to 18wt.% of ZnO where BaO+ZnO=4 to 24wt.%, is fused at about 1500 deg.C, then crushed in water to prepare small glass lumps of 1 to 3mm particle sizes (to deposite beta-wallastonite by heat treatment). Then, a glass plate about 5mm thick is coated with polyvinyl alcohol on its upper surface, then covered with the glass lumps in about 10mm thickness, and they are heated at about 1,000 deg.C for 2 hours. The resultant glass article is ground off by about 1mm thickness to bring about marble patterns.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a natural marble-like crystallized glass article used as an exterior material or an interior material for buildings and a method for producing the same.

[0002]

2. Description of the Related Art Crystallized glass articles having a natural marble pattern are widely known as exterior and interior materials for buildings.

Various types of crystallized glass have been proposed for this purpose. For example, in Japanese Patent Publication No. 53-39884, β-wollastonite (CaO.SiO ₂ ) is deposited as a main crystal. A crystallized glass obtained by the above is proposed, and JP-A-3-205323 discloses a crystallized glass obtained by depositing diopside (CaO.MgO.2SiO ₂ ) as a main crystal.

By the way, the natural marble-like crystallized glass article using the above-mentioned crystallized glass is an aggregation method, that is, a method in which a plurality of glass bodies are accumulated in a refractory mold and heat-treated to crystallize them. Manufactured in. This is because the above-mentioned crystallized glass does not contain any nucleating agent, and crystals are deposited almost vertically from the surface to the inside, that is, a so-called surface crystallized type of crystallized glass, and therefore, by a roll-out method or the like. This is because even if glass is molded into a plate shape and heat-treated to crystallize it, no pattern appears on the surface and a natural marble pattern cannot be obtained.

[0005]

However, the natural marble-like crystallized glass article produced by the agglomeration method has a low bending strength because a large number of bubbles trapped by the agglomeration remain inside, and the strength required as a building material. In order to obtain, the wall thickness must be increased. Therefore, it has the drawback of being very heavy and very difficult to construct.

[0006] It is an object of the present invention to provide a natural marble-like crystallized glass article which can be thinned and has a light weight because it has high bending strength, and a method for producing the same.

[0007]

A natural marble-like crystallized glass article according to the present invention comprises a glass plate on which a crystallized glass layer formed by fusing a plurality of glass bodies is formed. A natural marble-like crystallized glass article in which a crystal in a crystallized glass layer is regulated by the shape of the glass body, and a pattern appears based on the presence of the crystal and a difference in the direction thereof. The glass layer is (a) weight percent,
SiO ₂ 45-70%, Al ₂ O ₃ 1-13%, CaO
6-25%, Na ₂ O + K ₂ O + Li ₂ O 0.1-2
0%, BaO 0-20%, ZnO 0-18%, Ba
O + ZnO 4 to 24%, crystallized glass obtained by depositing β-wollastonite as a main crystal, or

(B) Percentage by weight of SiO ₂ 45-75
%, Al ₂ O ₃ 1-25%, CaO 1-20%, MgO
0.5-17%, BaO 0-18%, ZnO 0-
18%, Na ₂ O 1-15%, K ₂ O 0-7%, L
_{i 2 O 0~5%, B 2} O 3 0~10%, P 2 O 5 0~
10%, As ₂ O ₃ 0 to 1%, Sb ₂ O ₃ 0 to 1%, and is characterized by being made of crystallized glass in which diopside is deposited as a main crystal.

In the method for producing a natural marble-like crystallized glass article of the present invention, a plurality of glass bodies are accumulated on a glass plate and then heat-treated to fuse the glass bodies and the glass plates together. A method for producing a natural marble-like crystallized glass article, which comprises integrating crystals and precipitating crystals from the surface of the glass particles toward the inside thereof, wherein the glass particles are (a) a weight percentage of SiO ₂ 45- 70%, A
l ₂ O ₃ 1 to 13%, CaO 6 to 25%, Na ₂ O + K
₂ O + Li ₂ O 0.1-20%, BaO 0-20
%, ZnO 0-18%, BaO + ZnO 4-24%
Consisting of a crystalline glass having the property of precipitating β-wollastonite as a main crystal, or

(B) Percentage by weight of SiO ₂ 45-75
%, Al ₂ O ₃ 1-25%, CaO 1-20%, MgO
0.5-17%, BaO 0-18%, ZnO 0-
18%, Na ₂ O 1-15%, K ₂ O 0-7%, L
_{i 2 O 0~5%, B 2} O 3 0~10%, P 2 O 5 0~
A crystalline glass comprising 10%, As ₂ O ₃ 0 to 1% and Sb ₂ O ₃ 0 to 1% and having a property of precipitating diopside as a main crystal is used.

[0011]

In the natural marble-like crystallized glass article of the present invention, the crystals in the crystallized glass layer, that is, β-wollastonite and diopside are regulated by the shape of the glass bodies, and the presence of these crystals. And a natural marble-like pattern appears based on the difference in the direction. In addition, since the crystallized glass layer having such a pattern is formed on the glass plate, the crystallized glass article has high bending strength.

In the crystallized glass article of the present invention, if the glass plate is dense and has no bubbles, it may be composed of crystallized glass or amorphous glass, but it has higher bending strength. In order to obtain it, it is preferable to use one made of crystallized glass of volume crystallization type.

Next, in the crystallized glass article of the present invention,
The reason why the composition range of the crystallized glass of (a) and (b) used in the crystallized glass layer is limited as described above will be described.

Crystallized glass (a): SiO ₂ is a glass-forming component and a constituent component of β-wollastonite, and its content is 45 to 70%. SiO
_{When 2} is less than 45%, devitrification becomes high. Meanwhile 70%
The higher the amount, the higher the melting temperature of glass. Further, the viscosity increases and the fluidity at the time of heat treatment deteriorates, bubbles remain inside, the mechanical strength decreases, and a large amount of polishing is required to obtain a smooth surface.

Al ₂ O ₃ is a component for improving chemical durability, and its content is 1 to 13%. When Al ₂ O ₃ is less than 1%, devitrification becomes high and chemical durability is lowered. On the other hand, if it exceeds 13%, the viscosity of the glass increases and the stability of the color tone deteriorates.

CaO is a constituent of β-wollastonite, and its content is 6 to 25%. 6% CaO
If it is less, the amount of β-wollastonite deposited is reduced, the color stability is deteriorated, and the mechanical strength is reduced.
If it exceeds 25%, the amount of crystals becomes too large and the fluidity deteriorates.

Na ₂ O, K ₂ O and Li ₂ O are all flux agents, and the total content is 0.1 to 20%.
Is. If the total amount of these components is less than 0.1%, the viscosity increases and the flowability deteriorates, and if it exceeds 20%, the chemical durability deteriorates.

The content of BaO is 0 to 20%, and the content of ZnO is 0 to 18%. If the amount of each of these components is too large, β-wollastonite is hard to precipitate and desired properties cannot be obtained. The total amount of BaO and ZnO is 4
If it is less than 24%, the viscosity increases and the fluidity deteriorates.
%, Β-wollastonite is hard to precipitate.

Crystallized glass (b): SiO ₂ is a glass-forming component and a constituent of diopside, and its content is 45 to 75%. SiO ₂ is 45
If it is less than%, the devitrification becomes remarkable, and if it is more than 75%, the viscosity of the glass increases and the fluidity deteriorates.

Al ₂ O ₃ is a component that improves chemical durability, and its content is 1 to 25%. When Al ₂ O ₃ is less than 1%, the precipitated crystals become coarse and the flowability deteriorates, and when it exceeds 25%, the meltability deteriorates and diopside becomes difficult to precipitate.

CaO is a constituent of diopside and its content is 1 to 20%. If CaO is less than 1%, diopside will not be precipitated, and if it is more than 20%, the fluidity will be poor, and heterogeneous crystals will be precipitated, whereby desired characteristics cannot be obtained.

MgO is a constituent component of diopside, and its content is 0.5 to 17%. MgO is 0.
If it is less than 5%, diopside will be less likely to precipitate, and 1
If it exceeds 7%, the fluidity becomes poor.

BaO and ZnO are flux agents,
The content is 0 to 18%, respectively. When BaO or ZnO is more than 18%, diopside is hard to precipitate.

Na ₂ O is a fluxing agent, and its content is 1 to 15%. If the content of Na ₂ O is less than 1%, the fluidity will be poor, and if it is more than 15%, the chemical durability will be poor, and the coefficient of thermal expansion will be large, and the molded plate will be easily warped.

K ₂ O and Li ₂ O are flux agents like Na ₂ O, and their contents are 0 to 7% and 0 to 5%, respectively.
Is. If the amounts of K ₂ O and Li ₂ O are too large, the chemical durability deteriorates, and the coefficient of thermal expansion increases, so that the molded plate tends to warp.

B ₂ O ₃ and P ₂ O ₅ are components that improve the fluidity, and their contents are 0 to 10%, respectively. When B ₂ O ₃ and P ₂ O ₅ are more than 10%, diopside is hard to precipitate.

As ₂ O ₃ and Sb ₂ O ₃ can each be contained as refining agents up to 1%.

The crystallized glasses (a) and (b) are
In addition to the above-mentioned components, Fe ₂ O ₃ , NiO, Co
A natural marble-like crystallized glass article exhibiting a desired color tone can be obtained by adding a colored oxide such as O, Cr ₂ O ₃ , CuO, MnO ₂ , or V ₂ O ₅ .

Next, a method for producing the natural marble-like crystallized glass article of the present invention will be described.

First, a glass plate formed into a desired shape is prepared. The glass plate may be any of crystallized glass, crystallizable glass and amorphous glass as long as it is a bubble-free and dense one, but from the viewpoint of mechanical strength, volume crystallized type crystallized glass or crystallinity It is desirable to use glass.

A plurality of glass bodies made of crystalline glass having the composition (a) or (b) are prepared. The glass (a) or (b) used is a surface crystallization type crystalline glass having a property of precipitating crystals from the surface to the inside while softening and deforming when heat-treated at a temperature higher than the softening point. The glass small particles mean granulated glass, granules, powder, small spheres, small pieces, rod-shaped materials and the like.

Next, glass bodies are accumulated on the glass plate. At this time, it is important to collect glass bodies so as to completely cover the surface of the glass plate. Further, it is preferable to apply an adhesive such as polyvinyl alcohol (PVA) on the glass plate in advance, because the glass bodies can be fixed and the handling becomes easy.

Further, by heat-treating these at a temperature higher than the softening point, the glass small bodies, or both the glass small bodies and the glass plate are softened so that the glass small bodies and the glass plate are fused and integrated with each other. . At the same time, β-wollastonite and diopside are precipitated from the surface of the glass body toward the inside to form a crystallized glass layer in which a pattern appears due to the difference in the existence and direction of these crystals. When crystalline glass is used for the glass plate, it is crystallized at the same time.

It is important that the glass plate and the glass small body to be used are combined so that the coefficients of thermal expansion after heat treatment are approximately the same. Specifically, the difference in expansion between the two after heat treatment is 3 × 10 ^−. It is desirable to keep it within ⁷ / ° C.

[0035]

EXAMPLES The present invention will be described below based on Examples and Comparative Examples.

(Example 1) First, SiO ₂ 51.
0%, Al ₂ O ₃ 19.0%, MgO 4.7%, Zn
O 4.1%, TiO ₂ 2.2%, ZrO ₂ 1.5%,
B ₂ O ₃ 6.0%, Na ₂ O 8.5%, K ₂ O 2.
A glass raw material prepared so as to have a composition of 8% and CaO 0.2% was melted at 1500 ° C. for 16 hours, and then this molten glass was molded into a plate by a roll-out method.
A glass plate having a thickness of mm was obtained. This glass plate is
When heat-treated, the main crystals are forsterite (2MgO
· SiO ₂₎ to precipitate a crystalline glass having a thermal expansion coefficient is white crystallized glass of 67 × 10 ^-7 / ℃ at 30 to 380 ° C..

Further, SiO ₂ 65.1%, Al ₂ O ₃ 6.
6%, CaO 12.0%, Na ₂ O 3.3%, K ₂
A glass raw material prepared to have a composition of O 2.3%, BaO 4.1%, and ZnO 6.6% was melted at 1500 ° C. for 16 hours. Next, this molten glass was water-granulated, dried, and then classified to obtain glass bodies having a particle size of 1 to 3 mm. This glass small body is a crystalline glass which precipitates β-wollastonite as a main crystal when heat-treated and becomes a white crystallized glass having a thermal expansion coefficient of 65 × 10 ⁻⁷ / ° C. at 30 to 380 ° C.

Next, polyvinyl alcohol (PVA) was applied to the upper surface of the produced glass plate to completely cover the surface and accumulate the glass small bodies. The thickness of the integrated glass bodies was about 10 mm. Then, the temperature was raised at a rate of 60 ° C. for 1 hour, and the temperature was maintained at 1100 ° C. for 2 hours to obtain a crystallized glass article having a crystallized glass layer formed on the surface. The PVA applied to the glass plate disappeared during the heat treatment.

The crystallized glass article thus obtained had a thickness of about 10 mm, and when its surface was polished by about 1 mm, a white natural marble pattern appeared. Further, when the bending strength was measured, a value of 600 kgf / cm ² was shown. Further, as a result of X-ray diffraction, β-wollastonite was precipitated as a main crystal in the crystallized glass layer portion, and forsterite was precipitated as a main crystal in the glass plate portion.

For the bending strength, a sample having a size of 10 × 50 × 250 mm was used and a three-point bending method (span: 200 m
m).

Example 2 A glass plate produced in the same manner as in Example 1 was further heat-treated at 1000 ° C. for 1 hour to be crystallized.

Further, SiO ₂ 62.2%, Al ₂ O ₃ 5.
9%, CaO 12.9%, Na ₂ O 4.6%, K ₂
O 2.1%, Li ₂ O 1.0%, BaO 6.0
%, ZnO 5.2%, NiO 0.1% were mixed, and the glass raw material was melted at 1450 ° C. for 16 hours. Then, the molten glass was granulated, dried, and then classified to obtain a particle size. A glass body of 1 to 3 mm was obtained. This glass body precipitates β-wollastonite as a main crystal when heat-treated, and has a thermal expansion coefficient of 69 at 30 to 380 ° C.
It is a crystalline glass which becomes a beige crystallized glass having a density of × 10 ^-7 / ° C.

Then, PVA was coated on a glass plate in the same manner as in Example 1 to collect glass particles, and then the temperature was raised at a rate of 60 ° C. for 1 hour and the temperature was maintained at 1050 ° C. for 2 hours. A crystallized glass article having a crystallized glass layer formed on the surface was obtained.

When the crystallized glass article thus obtained was polished in the same manner as in Example 1, a beige natural marble pattern appeared. The bending strength is 620 kgf /
It was cm ² . The surface layer was precipitated with β-wollastonite as a main crystal, and the glass plate portion was precipitated with forsterite as a main crystal.

Example 3 First, SiO ₂ 52.
0%, Al ₂ O ₃ 17.0%, Na ₂ O 8.9%, C
aO 4.1%, TiO ₂ 3.5%, ZrO ₂ 1.4
%, B ₂ O ₃ 10.5%, P ₂ O ₅ 0.3%, K ₂ O
A glass raw material prepared so as to have a composition of 1.5%, BaO 0.5%, and Sb ₂ O ₃ 0.3% at 1450 ° C.
After melting for 6 hours, this molten glass was shaped into a plate by a roll-out method to obtain a glass plate having a thickness of 5 mm. The glass plate, when heat-treated to precipitate Jirukonoraito _{(CaO · ZrO 2 · 2TiO 2} ) as a main crystal, the thermal expansion coefficient of 70 × 10 ^-7 at 30 to 380 ° C.
It is a crystalline glass that becomes white crystallized glass at / ° C.

Further, SiO ₂ 62.0%, Al ₂ O ₃ 9.
0%, CaO 9.0%, MgO 4.5%, BaO
4.6%, Na ₂ O 5.0%, K ₂ O 3.0%, B
₂ O ₃ 0.5%, P ₂ O ₅ 2.0%, Sb ₂ O ₃ 0.4
%, CoO 0.05%, the glass raw material prepared was melted at 1500 ° C. for 16 hours, and then the molten glass was water granulated, dried, and then classified to have a particle diameter of 1 to 3 mm.
I got a glass body. When this glass body is heat-treated, diopsite is precipitated as a main crystal, and the glass body is 30 to 380 ° C.
Is a crystalline glass that becomes a gray crystallized glass having a coefficient of thermal expansion of 71 × 10 ⁻⁷ / ° C.

Next, Example 1 was placed on the upper surface of the produced glass plate.
After collecting glass bodies in the same manner as above, 60 ° C per hour
The temperature was raised at a rate of 1, and the temperature was maintained at 1050 ° C. for 2 hours to obtain a crystallized glass article having a crystallized glass layer formed on the surface.

When the surface of the crystallized glass article thus obtained was polished, a gray natural marble pattern appeared. The bending strength was 640 kgf / cm ² . In the precipitated crystal, the crystallized glass layer was diopside and the glass plate portion was zirconolite.

Example 4 First, in wt%, SiO ₂ 6
8.0%, Al ₂ O ₃ 4.8%, B ₂ O ₃ 16.0%,
CaO 1.5%, Na ₂ O 7.0%, K ₂ O 2.
A glass raw material prepared to have a composition of 3% and Sb ₂ O ₃ 0.4% was melted at 1400 ° C. for 16 hours, and then this molten glass was formed into a plate by a roll-out method,
A glass plate having a thickness of 5 mm was obtained. This glass plate is an amorphous glass having a coefficient of thermal expansion of 75 × 10 ⁻⁷ / ° C. at 30 to 380 ° C.

Further, SiO ₂ 60.0%, Al ₂ O ₃ 6.
0%, CaO 7.6%, MgO 3.8%, BaO
3.5%, ZnO 6.5%, Na ₂ O 3.8%, K
₂ O 2.5%, Li ₂ O 0.4%, B ₂ O ₃ 5.4
%, As ₂ O ₃ 0.3%, NiO 0.2% were mixed, the glass raw material was melted at 1500 ° C. for 16 hours, and then the molten glass was formed into a film, which was then crushed and classified. Then, a glass small body having a particle diameter of 1 to 3 mm was obtained. This glass body is a crystalline glass which becomes a beige-colored crystallized glass having a thermal expansion coefficient of 73 × 10 ⁻⁷ / ° C. at 30 to 380 ° C., which precipitates diopside as a main crystal when heat-treated.

Then, PVA was coated on a glass plate in the same manner as in Example 1 to collect glass particles, and then the temperature was raised at a rate of 60 ° C. for 1 hour and the temperature was kept at 1000 ° C. for 4 hours.
A crystallized glass article having a crystallized glass layer formed on the surface was obtained.

When the surface of the crystallized glass article thus obtained was polished, a beige natural marble pattern appeared. The bending strength was 580 kgf / cm ² . As a result of X-ray diffraction, diopside was precipitated as a main crystal in the crystallized glass layer.

(Comparative Example) The same small glass bodies as those used in Example 1 were collected and then heated at a rate of 60 ° C. for 1 hour and heat-treated at 1100 ° C. for 2 hours to obtain a film having a thickness of 10 mm. A crystallized glass article was obtained.

When the surface of the obtained crystallized glass was polished, a white natural marble pattern was obtained. As a result of X-ray diffraction, β-wollastonite was precipitated as the main crystal. However, the bending strength was 400 kgf / cm ² , which was considerably lower than that of the crystallized glass articles of Examples 1 to 4.

[0055]

As described above, since the natural marble-like crystallized glass article of the present invention has high bending strength, it can be used even if the wall thickness is thin. Therefore, it is lighter in weight and easier to construct than a natural marble-like crystallized glass article produced using a conventional integration method.

Further, according to the method for producing a natural marble-like crystallized glass article of the present invention, the crystallized glass article as described above can be easily produced. Further, it is possible to produce crystallized glass articles exhibiting various color tones by using glass bodies containing a colored oxide.

Claims (2)

[Claims] 1. A crystallized glass layer formed by fusing a plurality of glass particles on a glass plate, and the crystals in the crystallized glass layer are regulated by the shape of the glass particles. A natural marble-like crystallized glass article in which a pattern appears based on the presence of the crystals and a difference in the direction thereof, wherein the crystallized glass layer comprises (a) a weight percentage of Si:
O ₂ 45-70%, Al ₂ O ₃ 1-13%, CaO 6-
25%, Na ₂ O + K ₂ O + Li ₂ O 0.1-20
%, BaO 0-20%, ZnO 0-18%, BaO
+ ZnO 4 to 24% and crystallized glass formed by precipitating β-wollastonite as a main crystal, or (b)
In weight percentage, SiO ₂ 45-75%, Al ₂ O ₃₁ 1-
25%, CaO 1-20%, MgO 0.5-17%,
BaO 0-18%, ZnO 0-18%, Na ₂ O
1 to 15%, K ₂ O 0 to 7%, Li ₂ O 0 to 5%,
_{B 2 O 3 0~10%, P} 2 O 5 0~10%, As 2 O 3
A natural marble-like crystallized glass article comprising 0 to 1% and Sb ₂ O ₃ 0 to 1% and crystallized glass obtained by depositing diopside as a main crystal. 2. A plurality of glass bodies are collected on a glass plate and then heat-treated to fuse and integrate the glass bodies and the glass plate, and the glass bodies are directed from the surface to the inside. A method for producing a natural marble-like crystallized glass article, in which crystals are precipitated by using (a) a weight percentage of SiO ₂ 45-70%, Al
₂ O ₃ 1-13%, CaO 6-25%, Na ₂ O + K ₂
O + Li ₂ O 0.1-20%, BaO 0-20%,
ZnO 0 to 18%, BaO + ZnO 4 to 24%, crystalline glass having a property of precipitating β-wollastonite as a main crystal, or (b) a weight percentage of S,
iO ₂ 45-75%, Al ₂ O ₃ 1-25%, CaO 1
-20%, MgO 0.5-17%, BaO 0-18
%, ZnO 0-18%, Na ₂ O 1-15%, K ₂
O 0 to 7%, Li ₂ O 0 to 5%, B ₂ O ₃ 0 to 10
_{%, P 2 O 5 0~10%} , As 2 O 3 0~1%, Sb 2
A method for producing a natural marble-like crystallized glass article, characterized in that a crystalline glass comprising 0 to 1% of O ₃ and having a property of precipitating diopside as a main crystal is used.